CN102491293B - Method and device utilizing preparative chromatograph to separate krypton and xenon - Google Patents
Method and device utilizing preparative chromatograph to separate krypton and xenon Download PDFInfo
- Publication number
- CN102491293B CN102491293B CN 201110385067 CN201110385067A CN102491293B CN 102491293 B CN102491293 B CN 102491293B CN 201110385067 CN201110385067 CN 201110385067 CN 201110385067 A CN201110385067 A CN 201110385067A CN 102491293 B CN102491293 B CN 102491293B
- Authority
- CN
- China
- Prior art keywords
- xenon
- krypton
- preparative chromatography
- carrier gas
- chromatography post
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention relates to a method and a device utilizing a preparative chromatograph to separate krypton and xenon. The method comprises enabling a 5A molecular sieve to serve as a preparative chromatograph column, choosing appropriate carrier gas flow velocity and temperature of the chromatograph column by utilizing difference of the retention time of krypton and xenon on the chromatograph column, and achieving separation of krypton and xenon according to difference of the retention time of krypton and xenon on the chromatograph column. The separating device based on the method is reasonable in design and easy to operate, and can be used for nuclear fuel assembly monitoring, environmental monitoring and research evaluation.
Description
Technical field
The present invention relates to separation method and the device of rare gas krypton, xenon, take the 5A molecular sieve packed column as the preparative chromatography post, utilize the difference of krypton, xenon retention time on chromatographic column, select suitable flow rate of carrier gas and chromatogram column temperature, control krypton, the retention time of xenon on chromatographic column, realize the separation of krypton, xenon, the device that the method is set up can be used for nuclear fuel heap monitoring, environmental monitoring and research evaluation.
Background technology
Nuclear power plants, nuclear-propelled submarine etc. with
235U is the power reactor of nuclear fuel,
235Some radioactivity rare gas elementes that U fission produces as
85Kr,
88Kr,
133Xe and
135Xe etc., in the situation of clad breach, they can be diffused in the gas gap between fuel and the involucrum and finally discharge, and work the mischief.When carrying out radiometry, the part isotropic substance of radioactivity Kr can produce very large interference to the part isotropic substance of Xe, is Measurement accuracy, need to carry out the separation of Kr, Xe.
Literature search information: the people such as the German Alfred Wan Na of Linde AG invention number is the patent of CN1929455 " obtaining the method for krypton and/or xenon by the low ternperature separation process of air ", it is the air that to compress and to be cleaned, import to one and be used for the distillation system that nitrogen-oxygen separates, extract the enriched material of krypton-xenon-133 gas through devices such as high-pressure tower, lower pressure column, vaporizers.This patent need to be except the rectifying tower (knot screen) of deoxidation nitrogen, has methane to sneak at the mass transfer zone of first and second part of the second condenser-reboiler and lower pressure column, causes krypton, xenon concentrate to be mixed with impurity.In addition, the complex structure of this device, input cost is high, and methane is removed not exclusively in the krypton of high density, the xenon enriched product.63653 Feng of army of the Chinese People's Liberation Army are refined, and beautiful to wait people's invention number be the patent of 201010196384.0 " a kind of carbonaceous molecular sieve is used for the separation methods of radon and xenon ", and utilizing carbonaceous molecular sieve enrichment concentration is 40 * 10 for xenon standard gas and the activity of 20-200ppm
4-80 * 10
4Bq/m
3The radon gas body, entering the absorption of carbonaceous molecular sieve adsorption bed after removing moisture content through the 13X molecular sieve, the 13X sieve adsorpting bed of again flowing through behind the heating desorption is adsorbed on xenon, radon respectively on the carbonaceous molecular sieve adsorption bed of series connection, realizes the separation of xenon, radon.The method only can be separated the standard gas of xenon and radon; Tripping device has used Pyatyi adsorption bed, two kinds of sorbing materials, has increased complicacy and the operation easier of device; Carbonaceous molecular sieve activation treatment before use need the time long, operational condition is complicated; The sorbing material that this method is used is carbonaceous molecular sieve, the absorption that can not realize krypton and xenon with separate.
The present invention adopts the preparative chromatography post to realize krypton, xenon fractionation by adsorption.The method is take the 5A molecular sieve as sorbing material, adsorbs with being separated on the adsorption column to carry out, and selects optimal conditions that krypton, xenon are separated, realizes separating of krypton and xenon.Present method has broken through conventional Cyroadsorption, the Complicated Flow of the desorb that heats up step by step, and in addition, the preparative chromatography column conditioning time is short.Ingenious, simple in structure based on the design of the designed device of the method, operation is reliable, both can be used for the krypton in the places such as nuclear reactor, Nuclear power plants, the fractionation by adsorption of xenon, also can be environmental monitoring, Chemical Manufacture provides new technique means and measure.
Summary of the invention
The present invention proposes a kind of preparative chromatography for separating of the method and apparatus of krypton and xenon, because krypton, xenon concentration are low in the environment, physics and chemistry character approaches, and separates to have certain technical difficulty.Take the 5A molecular sieve packed column as the preparative chromatography post, utilize the difference of krypton, the xenon retention time on chromatographic column, select suitable flow rate of carrier gas and chromatogram column temperature, according to the difference of krypton, xenon retention time on chromatographic column, realize the separation of krypton, xenon.Based on the tripping device of this method, reasonable in design, simple to operation.
Solution of the present invention:
A kind of method of separating krypton and xenon with preparative chromatography may further comprise the steps
1] sample gas is written into the preparative chromatography post by carrier gas;
2] detect online the concentration that the preparative chromatography post flows out krypton and xenon;
3] according to online detected result, control flow rate of carrier gas and chromatogram column temperature, different according to krypton and the eluting peak of xenon on the preparative chromatography post are realized separating of krypton and xenon.
Above-mentioned flow rate of carrier gas is 70mL/min, and chromatogram column temperature is 120 ℃; The eluting peak of described krypton is 4.5～7.5min, and the eluting peak of described xenon is 8～14.5min.
A kind of device that separates krypton and xenon with preparative chromatography, comprise sample gas cylinder, carrier gas bottle, chromatogram quantification pipe, preparative chromatography post, collection container, thermal conductivity detector, mass flow controller, vacuum pump, its special character is: the threeway of described sample gas bottle graft, the chromatogram quantification pipe of wherein leading up to of described threeway links to each other with the inlet mouth of preparative chromatography post, and another road of described threeway links to each other with carrier gas bottle by mass flow controller; Described vacuum pump is connected to the import of preparative chromatography post by valve; The outlet of described preparative chromatography post connects threeway, and the valve of wherein leading up to of described threeway links to each other with thermal conductivity detector, and another road of described threeway connects six-way valve; A road of described six-way valve connects collection container, and another road is emptying.
Above-mentioned preparative chromatography post is copper pipe, its inner 60～80 order 5A molecular sieves of filling.
The working temperature of above-mentioned thermal conductivity detector is 150 ℃.
The carrier gas of above-mentioned carrier gas bottle is nitrogen or helium.
Technical characterstic of the present invention:
(1) chromatographic column is the copper pipe of long 4m, internal diameter 4mm, inner 60～80 order 5A molecular sieve 168g that fill.
(2) select by experiment suitable flow rate of carrier gas and chromatogram column temperature, the difference of krypton, xenon eluting peak (being retention time) on chromatographic column realizes the separation of krypton, xenon.
(3) utilize thermal conductivity detector to detect online, determine the elution time of krypton, xenon, real-time collecting krypton, xenon sample.
(4) the method to the rate of recovery of Kr, Xe all greater than 75%, to the decontamination factor of Kr＞5 * 10
2, to the decontamination factor of Xe＞2 * 10
3, obtained the higher sample of purity.
(5) the present invention only uses 5A molecular sieve chromatography post just to realize the separation of krypton, xenon, has reduced the complicacy of method and has realized difficulty.
Description of drawings
Fig. 1 is the structural representation that preparative chromatography is separated the device of krypton xenon;
Fig. 2 is krypton xenon separate colors spectrogram;
Wherein: 1-sample gas cylinder, 2-reducing valve, 3-threeway, 4-magnetic valve, 5-chromatogram quantification pipe, 6-magnetic valve, 7-valve, 8-vacuum pump, the 9-threeway, 10-preparative chromatography post, 11-pressure transmitter, 12-threeway, the 13-six-way valve, 14-collection container, 15-valve, 16-thermal conductivity detector, the 17-mass flow controller, 18-reducing valve, 19-carrier gas bottle, the 20-threeway, 21-mass flow controller, 22-valve.
Embodiment
Preparative chromatography of the present invention is for separating of the device of krypton and xenon, comprise the sample gas cylinder 1 that connects by pipeline, helium tank 19, chromatogram quantification pipe 5, preparative chromatography post 10, thermal conductivity detector 16, collection container 14, mass flow controller 17 and 21, magnetic valve 4,6 and vacuum pump 8, on the connecting tube of sample bottle 1 outlet, connecting successively reducing valve 2 and Y-junction 3, the pipeline that Y-junction 3 connects is divided into two-way, wherein connecting successively valve 22 on the first via pipeline, mass flow controller 21 and Y-junction 20, the two-way pipeline that Y-junction 20 is drawn is connecting respectively reducing valve 18, helium tank 19 and mass flow controller 17, the outlet of mass flow controller 17 is connecting thermal conductivity detector 16; Magnetic valve 4, chromatogram quantification pipe 5, magnetic valve 6 and Y-junction 9 are installed on the second road pipeline successively, what Y-junction 9 was told a road is connected with the valve 7 that is connected vacuum pump, another road of telling connects preparative chromatography post 10, pressure transmitter 11 and Y-junction 12 successively, the road pipeline that Y-junction 12 is told is connected with thermal conductivity detector 16 by valve 15, another road pipeline of telling is connecting six-way valve 13, this six-way valve 13 one tunnel is connecting collection container 14, and another road is emptying.
The principle of the invention:
The present invention utilizes the difference of fusing point and the boiling point of krypton, xenon take the 5A molecular sieve packed column as the preparative chromatography post, and the adsorption and desorption temperature on molecular sieve is different, realizes being separated from each other between them.Select suitable flow rate of carrier gas and chromatogram column temperature, according to the difference of krypton, xenon retention time on chromatographic column, realize the separation of krypton, xenon, carry out on-line monitoring with thermal conductivity detector, determine the collection time of krypton, xenon, and verify the separation efficiency of krypton, xenon.
According to annexation shown in Figure 1, set up the experimental installation that preparative chromatography is separated krypton, xenon.
Preparation 5A molecular sieve packed column, the copper pipe of long 4m, internal diameter 4mm, inner 60～80 order 5A molecular sieve 168g that fill.
The volume of chromatogram quantification pipe is 56.7mL.Take helium as carrier gas, take mass flow controller 21 control gas flow rates as 70mL/min, chromatogram column temperature is 120 ℃, and the thermal conductivity detector working temperature is 150 ℃, take mass flow controller 17 control reference gas velocities as 20mL/min.
Take 3 times of signal to noise ratios as standard, thermal conductivity detector is limited to 100ppm to the lowest detection of xenon, and the lowest detection of krypton is limited to 40ppm.
Operation steps:
Krypton in the chromatogram quantification pipe, xenon mixed gas (concentration be respectively 101,97.3ppm) are entered the preparative chromatography post with the helium carrier band, detect online the gaseous fraction that flows out chromatographic column with thermal conductivity detector, real-time collecting is investigated the separating effect of krypton, xenon.Separating resulting is controlled chromatogram column temperature and flow rate of carrier gas as shown in Figure 2, and the retention time of krypton, xenon has obvious difference, according to the difference of retention time, can realize separating of krypton and xenon.4.5 be the eluting peak of Kr between the～7.5min, be the eluting peak of Xe between 8～14.5min.
Experiment show:
4.5 collect Kr in the～7.5min, collect Xe in 8～14.5min.Respectively with steel cylinder collection, gas chromatographic measurement, according to steel cylinder volume, pressure and temperature, calculate recovery rate and decontamination factor the results are shown in Table 1 with Kr, Xe.Can find out that the rate of recovery of Kr, Xe is all greater than 75%, in the collected xenon sample to the decontamination factor of Kr＞5 * 10
2, in the krypton sample of collection to the decontamination factor of Xe＞2 * 10
3
Table 1 preparative chromatography is separated Kr, Xe result
Claims (4)
1. a method of separating krypton and xenon with preparative chromatography is characterized in that: may further comprise the steps
1] sample gas is written into the preparative chromatography post by carrier gas;
2] detect online the concentration that the preparative chromatography post flows out krypton and xenon;
3] according to online detected result, control flow rate of carrier gas and chromatogram column temperature, different according to krypton and the eluting peak of xenon on the preparative chromatography post are realized separating of krypton and xenon, and described flow rate of carrier gas is 70mL/min, and chromatogram column temperature is 120 ℃; The eluting peak of described krypton is 4.5～7.5 min, and the eluting peak of described xenon is 8～14.5 min.
2. device that separates krypton and xenon with preparative chromatography, comprise sample gas cylinder, carrier gas bottle, chromatogram quantification pipe, preparative chromatography post, collection container, thermal conductivity detector, mass flow controller, vacuum pump, it is characterized in that: the threeway of described sample gas bottle graft, the chromatogram quantification pipe of wherein leading up to of described threeway links to each other with the inlet mouth of preparative chromatography post, and another road of described threeway links to each other with carrier gas bottle by mass flow controller; Described vacuum pump is connected to the import of preparative chromatography post by valve; The outlet of described preparative chromatography post connects threeway, and the valve of wherein leading up to of described threeway links to each other with thermal conductivity detector, and another road of described threeway connects six-way valve; A road of described six-way valve connects collection container, and another road is emptying, and described preparative chromatography post is copper pipe, its inner 60～80 order 5A molecular sieves of filling.
3. according to claim 2ly separate the device of krypton and xenon with preparative chromatography, it is characterized in that: the working temperature of described thermal conductivity detector is 150 ℃.
4. according to claim 3ly separate the device of krypton and xenon with preparative chromatography, it is characterized in that: the carrier gas of described carrier gas bottle is nitrogen or helium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110385067 CN102491293B (en) | 2011-11-28 | 2011-11-28 | Method and device utilizing preparative chromatograph to separate krypton and xenon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110385067 CN102491293B (en) | 2011-11-28 | 2011-11-28 | Method and device utilizing preparative chromatograph to separate krypton and xenon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102491293A CN102491293A (en) | 2012-06-13 |
| CN102491293B true CN102491293B (en) | 2013-10-30 |
Family
ID=46183164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110385067 Expired - Fee Related CN102491293B (en) | 2011-11-28 | 2011-11-28 | Method and device utilizing preparative chromatograph to separate krypton and xenon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102491293B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103487543B (en) * | 2013-09-17 | 2015-08-05 | 武汉钢铁(集团)公司 | The analytical approach of Krypton and xenon content in krypton xenon unstripped gas |
| CN106215621B (en) * | 2016-09-19 | 2018-10-16 | 中国矿业大学 | A kind of methane adsorption concentration systems for extremely low concentration mash gas extraction |
| US20210213220A1 (en) | 2018-05-29 | 2021-07-15 | Sagetech Medical Equipment Limited | Capture of xenon from anaesthetic gas and re-administration thereof to the patient |
| CN109939538B (en) * | 2019-04-12 | 2020-07-28 | 中国原子能科学研究院 | System and method for rapidly separating Kr and Xe in complex fission product |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1420079A (en) * | 2001-11-19 | 2003-05-28 | 气体产品与化学公司 | Method and adsorbent for recovering kryptsn and xenon from gas stream or liquid stream |
-
2011
- 2011-11-28 CN CN 201110385067 patent/CN102491293B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1420079A (en) * | 2001-11-19 | 2003-05-28 | 气体产品与化学公司 | Method and adsorbent for recovering kryptsn and xenon from gas stream or liquid stream |
Non-Patent Citations (2)
| Title |
|---|
| 放射性氙分离纯化技术;王茜等;《核化学与放射化学》;20110831;第33卷(第4期);第230-235页 * |
| 王茜等.放射性氙分离纯化技术.《核化学与放射化学》.2011,第33卷(第4期),第230-235页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102491293A (en) | 2012-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104340959B (en) | A kind of hydrogen helium gas mixture body is separated and retrieving arrangement | |
| CN202052451U (en) | Device for enriching and separating xenon in air through carbon molecular sieves | |
| CN201110847Y (en) | Adsorbing agent voltage transformation adsorptive separation performance test and infiltration flow experimental device | |
| CN102491293B (en) | Method and device utilizing preparative chromatograph to separate krypton and xenon | |
| CN102359895B (en) | Normal temperature enrichment and sampling method for xenon in air | |
| CN103048412B (en) | Online analysis pretreatment device for trace hydrogen isotopes in natural gas | |
| EP2326408B1 (en) | Process for the enrichment of isotopes | |
| CN102389683B (en) | Method and device for separating krypton from xenon by using active carbon | |
| CN102508285B (en) | Method and device for enriching and sampling xenon in atmosphere at low temperature | |
| CN201728039U (en) | Separating device with enrichment of gaseous xenon | |
| CN104931615B (en) | Analysis of Micro-amount Impurities In Liquid device and method in a kind of gas | |
| CN101985080A (en) | Method for enriching and separating xenon by using activated carbon | |
| Riedmann et al. | Separation of argon from environmental samples for Ar-37 and Ar-39 analyses | |
| Topin et al. | SPALAX new generation: New process design for a more efficient xenon production system for the CTBT noble gas network | |
| CN107930400A (en) | A kind of hydrogen helium separation and hydrogen isotope concentration coupled system and method | |
| CN104383784B (en) | The system and method for separation and Extraction inert gas from environmental gas | |
| CN111579694A (en) | System and method for analyzing content of trace impurities in deuterium-tritium mixed gas | |
| CN107561177B (en) | Continuous monitoring device and method for radioactive gas | |
| CN112892211B (en) | Column type hydrogen helium separation and concentration coupling device and method | |
| Dong et al. | Dual separation of krypton and argon from environmental samples for radioisotope dating | |
| CN205844286U (en) | Microliter amount gas unimolecule stability of compounds isotopics analytical equipment | |
| CN205941482U (en) | Krypton in nuclear facilities gas year effluent 85 measuring separator | |
| CN102489108B (en) | Method for separating and purifying xenon in atmosphere by use of active carbon and device thereof | |
| CN201637728U (en) | Device for rapidly detecting constituents of hydrogen | |
| CN102004133A (en) | Gas chromatography for analyzing methane and nitrous oxide in air by one sample injection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131030 Termination date: 20171128 |